(1R,3R,4S,6R,7R,9R)-4-bromo-3-ethyl-9-(3-phenylmethoxypropyl)-2,8-dioxabicyclo[5.2.1]decan-6-ol | 1093122-02-1

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (1R,3R,4S,6R,7R,9R)-4-bromo-3-ethyl-9-(3-phenylmethoxypropyl)-2,8-dioxabicyclo[5.2.1]decan-6-ol
• CAS: 1093122-02-1
• 化学式: C₂₀H₂₉BrO₄
• 分子量: 413.352
• InChiKey: KLBJEYJXPZBGIY-RFVXBFLTSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  25
• 可旋转键数：
  7
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.7
• 拓扑面积：
  47.9
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (1R,3R,4S,6R,7R,9R)-4-bromo-3-ethyl-9-(3-phenylmethoxypropyl)-2,8-dioxabicyclo[5.2.1]decan-6-ol 在 palladium 10% on activated carbon 、 氢气 作用下， 以 乙醇 为溶剂， 反应 0.5h， 以100%的产率得到
  参考文献：
  名称：

  Biomimetic Asymmetric Total Synthesis of (−)-Laurefucin via an Organoselenium-Mediated Intramolecular Hydroxyetherification

  摘要：

  The first asymmetric total synthesis of (-)-laurefucin (1), a unique C-15 acetogenin with a 2,8-dioxabicyclo[5.2.1]decane skeleton, has been accomplished in nine steps in 31% overall yield from known oxocene 10. Highlights of the highly stereoselective synthesis include a novel organoselenium-mediated biomimetic hydroxyetherification.

  DOI：

  10.1021/ja806304s
• 作为产物：
  描述：

  (R)-4-(benzyloxy)-1-((2R,7S,8R)-7-bromo-8-ethyl-3,6,7,8-tetrahydro-2H-oxocin-2-yl)butan-1-ol 在 N-(苯硒基)邻苯二甲酰亚胺 、 水 、 对甲苯磺酸 作用下， 以 乙腈 为溶剂， 反应 2.5h， 以100%的产率得到(1R,3R,4S,6R,7R,9R)-4-bromo-3-ethyl-9-(3-phenylmethoxypropyl)-2,8-dioxabicyclo[5.2.1]decan-6-ol
  参考文献：
  名称：

  Biomimetic Asymmetric Total Synthesis of (−)-Laurefucin via an Organoselenium-Mediated Intramolecular Hydroxyetherification

  摘要：

  The first asymmetric total synthesis of (-)-laurefucin (1), a unique C-15 acetogenin with a 2,8-dioxabicyclo[5.2.1]decane skeleton, has been accomplished in nine steps in 31% overall yield from known oxocene 10. Highlights of the highly stereoselective synthesis include a novel organoselenium-mediated biomimetic hydroxyetherification.

  DOI：

  10.1021/ja806304s

文献信息

• Biomimetic Asymmetric Total Synthesis of (−)-Laurefucin via an Organoselenium-Mediated Intramolecular Hydroxyetherification
  作者：Byungsook Kim、Miseon Lee、Mi Jung Kim、Hyunjoo Lee、Sanghee Kim、Deukjoon Kim、Minseob Koh、Seung Bum Park、Kye Jung Shin

  DOI：10.1021/ja806304s

  日期：2008.12.10

  The first asymmetric total synthesis of (-)-laurefucin (1), a unique C-15 acetogenin with a 2,8-dioxabicyclo[5.2.1]decane skeleton, has been accomplished in nine steps in 31% overall yield from known oxocene 10. Highlights of the highly stereoselective synthesis include a novel organoselenium-mediated biomimetic hydroxyetherification.
• Asymmetric Total Synthesis and Structure Confirmation of (+)-(3E)-Isolaurefucin Methyl Ether
  作者：Deukjoon Kim、Te-ik Sohn、Byungsook Kim、Robert S. Paton

  DOI：10.3987/com-17-s(t)1

  日期：——

  An asymmetric total synthesis and structure confirmation of (+)-(3E)-isolaurefucin methyl ether (2a) was accomplished. Our synthesis features two complementary routes to construct the alpha,alpha'-trans-2,8-dioxabicyclo[5.2.1]decane skeleton of the natural product from alpha,alpha'-trans-gamma,delta-unsaturated oxocene alcohol 7, namely, an intramolecular epoxide opening route and a novel methoxyetherification route based on organoseleniummediated oxonium ion formation/fragmentation. A computational analysis was performed to model the observed different fragmentation behaviors of the respective oxonium ions 8 and 8' derived from alpha,alpha'-trans- and alpha,alpha'-cis-gamma,delta-unsaturated oxocene alcohols 7 and 7' during the organoselenium-mediated oxonium ion formation/fragmentation. Regarding the possibility of the natural product being an artifact, the reactivity of chlorofucin surrogate 16 and neoprelaurefucin surrogate 16' during methanolysis was compared, the results were in good agreement with calculations.